JP2000053950A - Water repellent preparation based on fluoroalkylalkoxysilane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an economical water repellent preparation exhibiting high performance unattainable by conventional water repellent preparations, by using an alkoxysilane compound including a perfluoro group having a new structure as the indispensable component. SOLUTION: This water repellant preparation includes a fluoroalkylalkoxysilane in which the N atom of an aminoalkoxysilane expressed by the following formula I has at least one monovalent bonding group expressed by the following formula II. Formula I; HN(R')-Y-Si(R)a(X)3-a (R' is H or a monovalent hydrocarbon group, R is a monovalent hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group or -(CH2)y-NH-Y', Y' is a divalent hydrocarbon group, (y) is an integer of 1 to 4, (a) is an integer of 0 to 2). Formula II; CnF2n+1-CxH2X-O-CH2-CH(OH)-CH2- ((n) is an integer of 1<=n<=23, (x) is 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water repellent comprising a novel fluoroalkylalkoxysilane compound as an essential component. More specifically, the present invention relates to a water repellent containing a novel fluoroalkylalkoxysilane compound as an essential component, which is excellent in stability, durability and can impart excellent water repellency to a substrate surface. .

[0002]

2. Description of the Related Art In recent years, various uses of perfluoroalkanes have been proposed as techniques for modifying the properties and functions of solid surfaces. Regarding the use of the perfluoroalkane, processing (resin processing) using a so-called fluororesin (commonly known as Teflon) centered on tetrafluoroethylene has been known for a long time.

On the other hand, attempts have been made to directly use perfluoroalkanes in order to improve the water repellency and antifouling properties of the substrate surface. For example, a solution of perfluoroalkane or an alcohol derivative thereof is used as a substrate. The method of spraying and applying to the surface is adopted. However, the method of directly using perfluoroalkanes is effective for temporary water repellency of clothes, for example, but is removed by cleaning or the like, so that a stable and permanent effect can be obtained. Have difficulty.

In such a background, as a permanent treatment method for maintaining a water repellent effect, a water repellent using a perfluoroalkoxysilane, for example, a perfluoroalkoxysilane represented by the following general formula (8): Compositions have been proposed (JP-A-8-218060, JP-A-9-130).
No. 17, 9-169779, and 9-176622).

<General formula (8)> C _n F _{2n + 1} -Y'-Si (R) _a (X) _3-a (8) (where n, a, R and X are the same as those described above.
Y ′ represents a divalent hydrocarbon group. )

However, the perfluoroalkoxysilane represented by the general formula (8) has, for example, insufficient adhesion on a glass surface and poor water repellency by itself. Or a pretreatment with tetraethyl silicate or the like is required.

On the other hand, various methods have been proposed for producing a new perfluoro group-containing silicon compound by introducing an alkoxysilane into a perfluoroalkane compound. However, when providing an organosilicon compound having a new structure, it is an important subject to introduce it as a [—Si—C—] bond in a molecular chain. This is [-Si-OC-]
In an organosilicon compound having a bond, (-S
This is because hydrolysis tends to occur between the bonds of i-) and (-OC-), and such bonds should be excluded from the main structure. Incidentally, alkoxysilanes and the like having [-Si-OC-] bonds are used as hydrolyzable condensation reaction groups (active sites).

In the method for producing an organosilicon compound by reacting an organic group with a silicon compound, the [-Z] portion of the [-Si-Z] bond portion (where Z represents a hydrogen atom or a halogen atom) is replaced with an organic compound. A method of performing a substitution reaction with a group is employed. In this case, the [-Si-Z] bond is generally disproportionated or redistributed.
It is reported by Anderson and others that it is easy to form a disordered equilibrium mixture by a reaction called "action reaction", which is a characteristic feature of the reactivity of organosilicon compounds. ,
Issued October 3, 1959).

The above-mentioned disordered equilibrium mixture is, for example, when an alkoxysilane is produced by reacting a fluoroalkyltrichlorosilane with a monovalent saturated alcohol, -SiCl ₃ / -SiCl ₂ (X) /-SiCl by the equilibrium reaction. (X)
The production ratio of ₂ / -Si (X) ₃ differs depending on the reaction conditions, the use ratio of the fluoroalkyltrichlorosilane and the saturated alcohol, and the like. When the ratio is 1: 3 (molar ratio),
It is easy to converge approximately (1/3/3/1). For this reason, in this type of reaction, dehalogenation is an important subject, and it is necessary to carry out dehalogenation with a large amount of inert gas or to employ a special technique (see JP-A-9-169779). ).

[0010] Therefore, in order to obtain a desired product by the above-mentioned reaction, strict separation is required by distillation or the like, and it is extremely difficult to obtain a single component.
Therefore, there is a strong demand in the art for a production technique capable of obtaining an organosilicon compound of a single component alkoxysilane.

[0011]

SUMMARY OF THE INVENTION In view of the above-mentioned limitations of the prior art, the present invention is to provide a water repellent containing an organosilicon compound, particularly a fluoroalkylalkoxysilane compound having a new structure as an essential component. is there.

In particular, the present invention has an affinity for the surface of various substrates and a property of firmly binding,
Further, an object of the present invention is to provide a water repellent containing, as an essential component, a perfluoroalkyl group-containing perfluoroalkylalkoxysilane compound having a novel structure capable of imparting excellent water repellency to a substrate surface. .

Still further, the present invention provides an efficient and economical method for producing the above-mentioned perfluoroalkylalkoxysilane compound having a new structure by avoiding disproportionation and redistribution reactions encountered in conventional production techniques. Therefore, it is an object of the present invention to provide a novel water repellent agent which can achieve both improvement in water repellency characteristics and economic efficiency.

[0014]

The present invention is summarized as follows. According to a first aspect of the present invention, the N atom of the aminoalkoxysilane compound represented by the following general formula (1) is represented by the following general formula:
The present invention relates to a water repellent comprising a fluoroalkylalkoxysilane compound having at least one monovalent bonding group represented by (2). <General formula (1)> HN (R ')-Y-Si (R) _a (X) _3-a ............ (1) (In the formula, R' is hydrogen or monovalent. R is a monovalent hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group or — (CH ₂ ) _y —NH—Y ′, Y ′ is a divalent hydrocarbon group,
y represents an integer of 1 to 4, and a represents an integer of 0 to 2. ) <Formula _{(2)> C n F 2n} + 1 -C x H 2x -O-CH 2 -CH (OH) -CH 2 - ............... (2) ( wherein, n 1 ≦ n <An integer of 23, and x represents an integer of 1 or 2.)

In a second aspect of the present invention, two molecules of an aminoalkoxysilane compound represented by the following general formula (1) are represented by the following general formula (3) via respective N atoms. The present invention relates to a water repellent comprising a fluoroalkylalkoxysilane compound which is bonded to a divalent bonding group. <General formula (1)> HN (R ')-Y-Si (R) _a (X) _3-a ............ (1) (In the formula, R' is hydrogen or monovalent. R is a monovalent hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group or — (CH ₂ ) _y —NH—Y ′, Y ′ is a divalent hydrocarbon group. , y is an integer from 1 to 4, a is an integer of 0 to 2.) <formula _{(3)> [-CH 2 -CH} (OH) -CH 2 -O-C n H 2n -C x F _2x —O—CH ₂ —CH (OH) —CH ₂ —] (3) (where n is an integer of 1 ≦ n <23, and x is 1 or 2 Indicates an integer.)

The fluoroalkylalkoxysilane compound defined in the invention of the first and second water repellents of the present invention is more specifically represented by the following general formulas (4) to (5). is there. The water repellent of the present invention comprises at least one fluoroalkylalkoxysilane compound represented by the following general formulas (4) to (5).

[0017] <Formula _{(4)> C n F 2n} + 1 -C x H 2x -O-CH 2 -CH (OH) -CH 2 -N (R ') - Y-Si (R) a (X ) _3-a ... (4) (wherein R ', R, X, Y and a are the same as those described above)

<General formula (5)> (X) _3-a (R) _a Si—Y—N (R ′) — CH ₂ —CH (OH) —CH ₂ —O—C _x H _2x —C _n F _2n —C _x H _2x —O—CH ₂ —CH (OH) —CH ₂ —N (R ′) — Y—Si (R) _a (X) _3-a ………………………… (5) (In the formula, R ′, R, X, Y, n, x, and a are the same as those described above.)

Further, the present invention relates to the above-mentioned general formulas (4) to (5)
The present invention also relates to the invention of a water repellent comprising a fluoroalkylalkoxysilane compound represented by the following formula (1) as an essential component, in which a novel substance as an essential component is defined by a product-by-process.

In the invention of the water-repellent agent of the present invention, which comprises a fluoroalkylalkoxysilane compound having a novel structure represented by the general formula (4) as an essential component, the method for producing the novel fluoroalkylalkoxysilane is outlined below. And an aminoalkoxysilane represented by the following general formula (1) in an alcohol solvent: <General formula (1)> HN (R ′)-Y—Si (R) _a (X) _3-a ... (1) (wherein, R ', R, X, Y, and a are the same as those described above.) A fluoroalkyl group-containing epoxy represented by the following general formula (6) It is characterized by reacting a compound.

[0021]

Embedded image (In the formula, n and x are the same as described above.)

In the invention of the water repellent of the present invention, which comprises a fluoroalkylalkoxysilane compound having a novel structure represented by the above general formula (5) as an essential component, the method for producing the novel fluoroalkylalkoxysilane is outlined below. And an aminoalkoxysilane represented by the following general formula (1) in an alcohol solvent: <General formula (1)> HN (R ′)-Y—Si (R) _a (X) _3-a ... (1) (wherein, R ', R, X, Y, and a are the same as those described above.) A fluoroalkyl group-containing diepoxy represented by the following general formula (7) It is characterized by reacting a compound.

[0023]

Embedded image (In the formula, n and x are the same as described above.)

Hereinafter, the technical structure and embodiments of the present invention will be described in detail.

[0025] In an essential component of the water repellent agent of the present _{invention, [C n F 2 n +} 1 -C in formula (2) and (4) _x H _2x -O
- portion of] the perfluoro alcohol, C _n F _{2n + 1} -
It can be given by C _x H _2x -OH. As the perfluoroalcohol, those wherein n is 1 ≦ n <23 are currently available.

In the present invention, the n-value of the perfluoroalcohol is such that as the n-value increases, the perfluoroalkyl group in the side chain overlaps the surface of the substrate and exhibits the same properties as when introduced into the main chain. Although lubricity can be expected, it is difficult to select a solvent. Therefore, in the present invention, the n value is preferably about 1 ≦ n <17.

[0027] In an essential component of the water repellent agent of the present invention, the general formula (2) and [in _{(4) C n F 2 n} + 1 -C x H 2x -O-
CH ₂ —CH (OH) —CH ₂ —] is represented by the following general formula (6) prepared by reacting the perfluoroalcohol (C _n F _{2n + 1} —C _x H _2x —OH) with epichlorohydrin. It can be provided by the indicated fluoroalkyl-containing epoxy compound, ie, perfluoroalkanol glycidyl ether.

<General formula (6)>

Embedded image (In the formula, n and x are the same as described above.)

The general formula which is an essential component of the water repellent of the present invention
The fluoroalkylalkoxysilane compound represented by (4) includes a fluoroalkyl group-containing epoxy compound (perfluoroalkanol glycidyl ether) represented by the general formula (6) and an aminoalkoxysilane compound represented by the general formula (1). Prepared by paying attention to the reactivity of In the present invention, the aminoalkoxysilane represented by the general formula (1) is easily available and has excellent reactivity with perfluoroalkanol glycidyl ether. In the aminoalkoxysilane represented by the general formula (1), (R ′) represents hydrogen or a monovalent hydrocarbon, and the monovalent hydrocarbon group is a lower group such as a methyl group, an ethyl group, and a propyl group. An alkyl group is exemplified.

The reaction for producing the perfluoroalkanol glycidyl ether represented by the general formula (6) and the general formula (1)
The reaction with an aminoalkoxysilane represented by the following formula can be represented by the following formula. Needless to say, the compound synthesized by the above reaction is a fluoroalkylalkoxysilane compound represented by the general formula (4) of the present invention.

[0031]

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In the present invention, the reaction between the perfluoroalkanol glycidyl ether and the aminoalkoxysilane represented by the above formula (Chem. 6) has an advantage that it proceeds very smoothly (easily) at room temperature in an alcohol solvent. In the present invention, the above-mentioned reaction will be described in detail later, but the reaction may be carried out by heating to a boiling point or lower of the reaction solvent used.

The first feature of the present invention is, as apparent from the above, that the N atom of the aminoalkoxysilane compound represented by the general formula (1) is represented by the general formula (2). A novel substance comprising a fluoroalkylalkoxysilane compound having at least one monovalent bonding group as a side chain is an essential component of the water repellent. The second characteristic point of the present invention is that it can be easily inferred from the first characteristic point. However, the second characteristic point represented by the general formula (3) similar to the general formula (2) in the molecular chain. A novel substance comprising a fluoroalkylalkoxysilane having a valence bonding group is used as an essential component of the water repellent.

The aminoalkoxysilane compound represented by the general formula (1), which is an essential component of the water repellent of the present invention, has an N atom having a monovalent bonding group represented by the general formula (2). The fluoroalkylalkoxysilane compound represented by (4) will be described in detail. The production and properties of other novel compounds of the present invention are described in the following general formula.
It can be easily understood in relation to the novel compound shown in (4).

Among the compounds represented by the general formula (4), which are essential components of the water repellent of the present invention, representative examples include
The fluoroalkylalkoxysilane compound having a new structure synthesized by the reaction of 3-aminopropylalkoxysilane with perfluoroalkanol glycidyl ether will be described in detail.

The present inventors have selected (i) 3-aminopropyltriethoxysilane and H ₂ N— (CH ₂ ) ₃ —Si (OEt) ₃ as the aminoalkoxysilane represented by the general formula (1). And (ii) as a perfluoroalkanol glycidyl ether represented by the general formula (6), n = 8, x
= 1 and the following reaction was carried out.

[0037]

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In the above reaction formula (Formula 7), (i) the amino group (—NH ₂ ) of aminopropyltriethoxysilane
Has two active hydrogens, it is considered that two moles of glycidyl groups are consumed in a general organic reaction, but (ii). It was observed that hydrogen reacts preferentially, and thus one molecule of glycidyl group is selectively added to one molecule of aminosilane. In the above reaction process, in an equimolar reaction between aminoalkoxysilane and perfluoroalkanol glycidyl ether (hereinafter abbreviated as PFAG), TLC (thin layer chromatography) of a reaction product is performed.
Was analyzed, it was proved that unreacted aminoalkoxysilane was not detected.

However, in the present invention, the reaction is carried out in the presence of excess PFAG,
When the reaction is carried out using an excess amount of the primary amine, it reacts with two hydrogens of the primary amine, or when the aminoalkoxysilane is diaminosilane (secondary amine), the secondary amine and PFAG are consumed after the primary amine is consumed. Was found to react. It is considered that whether 1 mol or 2 mol or more of PFAG is added to 1 mol of aminoalkoxysilane is due to the structure of the aminoalkoxysilane used and the steric hindrance of PFAG. Can be

In the present invention, examples of the compound obtained by adding 2 mol of PFAG to 1 mol of aminoalkoxysilane include those represented by the following general formula (9). <Formula _{(9)> [C n F} 2n + 1 -C x H 2x -O-CH 2 -CH (OH) -CH 2] 2 N-Y-Si (R) a (X) 3-a ... …………………… (9)

In the present invention, the knowledge obtained from the observation of the reaction process represented by the above-mentioned reaction formula (Formula 7) is useful for specifying the type of aminoalkoxysilane to be used. That is, as is apparent from the above, in the present invention, not only primary amines but also a mixture of primary amines and secondary amines can be used as aminoalkoxysilanes.

In the present invention, aminoalkoxysilane in which primary amine and secondary amine are mixed, more specifically,
When H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OMe) ₃ or the like is used (Me indicates a methyl group), first, PFAG is a molecular terminal as shown in the following (Chem. 8). Was confirmed to react preferentially with the primary amine.

[0043]

Embedded image

In the present invention, the reaction between the PFAG and the aminoalkoxysilane proceeds in an alcohol solvent at room temperature or under the boiling point of the alcohol without using any special catalyst.

In the reaction of the PFAG with the aminoalkoxysilane of the present invention, the reaction atmosphere is preferably under a nitrogen atmosphere, and the alcohol (reaction medium) used
Also preferred is dehydrated alcohol.

In the present invention, as the alcohol used as the reaction medium, an alcohol having an alkoxy group of the same kind as the alkoxy group of the aminoalkoxysilane is used.
%, Preferably at least 20%. In this case, during the reaction, a condensation reaction due to hydrolysis of the alkoxy group can be suppressed.

On the other hand, the present invention relates to the purpose of using the novel compound of the present invention, when a hydrolyzate oligomer (dimer, trimer, etc.) is intentionally used, a small amount of water is added, An oligomer can be obtained by condensing a part of the alkoxy.
In this case, a desired solvent such as toluene, xylene, acetone or methyl ethyl ketone can be used as a reaction medium at a ratio of 50% or less.

Next, the general formula (5) having a divalent bonding group represented by the general formula (3), which is an essential component of the water repellent of the present invention,
Will be described. The essential component of the water repellent of the present invention has a novel structure in the side chain represented by the general formula (4) or the general formula (9) having a monovalent bonding group represented by the general formula (2) as described above. Is not limited to a compound having a perfluoroalkyl group introduced therein,
It also relates to a compound having a group similar to these introduced into the main chain.

The fluoroalkylalkoxysilane compound represented by the general formula (5), which is an essential component of the water repellent of the present invention, can be easily prepared because its starting material, perfluoroalkanol, is easy to prepare. Can be. For example, the starting material perfluoroalkanol can be easily prepared by fluorinating, hydrolyzing, and reducing an aliphatic alkyl ester such as an aliphatic methyl ester. Furthermore, a perfluoroalkanediol represented by the following general formula (10) is obtained by fluorinating, hydrolyzing, and reducing an aliphatic diester such as an aliphatic dimethyl ester. In <formula _{(10)> HO-C x} H 2x -C n F 2n -C x H 2x -OH .............................. (10) present invention, represented by formula (5) The fluoroalkylalkoxysilane compound can be prepared using one or more of the above-mentioned perfluoroalkanols and perfluoroalkanediols.

Next, by adding epichlorohydrin to the perfluoroalkanediol represented by the general formula (10), for example,
A fluoroalkyl group-containing diepoxy compound represented by (7) can be prepared.

<General formula (7)>

Embedded image (In the formula, n and x are the same as described above.)

Further, by reacting the fluoroalkyl group-containing epoxy compound represented by the general formula (7) with the aminoalkoxysilane (aminosilane) represented by the general formula (1), the compound represented by the general formula (5) ), A fluoroalkylalkoxysilane compound having a new structure in which a perfluoroalkylene chain is introduced into the main chain can be prepared. <Formula _{(5)> (X) 3} -a (R) a Si-Y-N (R ') - CH 2 -CH (OH) -CH 2 -O-C x H 2x - C n F 2n - C _x H _2x —O—CH ₂ —CH (OH) —CH ₂ —N (R ′) — Y—Si (R) _a (X) _3-a ………………… (5)

In the present invention, the fluoroalkylalkoxysilane compound having a perfluoroalkylene chain introduced into the main chain represented by the general formula (5) is a compound represented by the general formula (5).
They are also useful as those introduced into the side chain shown in (4). When a substance having a perfluoroalkylene chain introduced into the main chain is used as a water-repellent, durability and water-repellent performance tend to decrease as the value of n increases. For this reason, it is preferable to set the n value lower, for example, to 4 or less. In the present invention, (i) a perfluoroalkyl group represented by the general formula (4) in the side chain, and (ii) a perfluoroalkylene chain represented by the general formula (5) Can be used alone or in combination.

The following are starting materials applied to the production of the fluoroalkylalkoxysilane compound represented by the general formula (4) to (5) or the general formula (9), which is an essential component of the water repellent of the present invention. (i) Aminoalkoxysilane represented by the general formula (1) and (ii) Perfluoroalkanol glycidyl ether (PFAG) represented by the general formula (6) will be described in more detail.

(I) The aminoalkoxysilane represented by the general formula (1): The aminoalkoxysilane represented by the general formula (1) used in the production of the essential component of the water repellent of the present invention is as follows: Things can be exemplified. (1) 3-Aminopropyltrimethoxysilane (2) 3-Aminopropyltriethoxysilane (3) 3-Aminopropylmethyldimethoxysilane (4) .3-Aminopropylmethyldiethoxysilane (5) .H _{2 N- (CH 2) 2 -N} (CH 2 CH = CH) - (CH 2) 3
-Si (OMe) ₃ 3- [N- Allyl -N (aminoethyl)] aminopropyltrimethoxysilane _{(6) .H 2 N- (CH} 2) 2 -NH-CH 2 - (C 6 H 4) - (C
_{H 2) 2 -Si (OMe)} 3 P [N (2- aminoethyl) aminomethyl] phenethyltrimethoxysilane _{(7) .H 2 N- (CH} 2) 2 -NH- (CH 2) 3 -Si ( Me) (OM
e) ₂ N (2-aminoethyl) -3-aminopropyl methyl dimethoxy silane _{(8) .H 2 N- (CH} 2) 2 -NH- (CH 2) 3 -Si (OMe) 3 N (2- Amino Ethyl) -3-aminopropyltrimethoxysilane

(Ii) Perfluoroalkanol glycidyl ether (PFAG) represented by the general formula (6): The above general formula used in the production of the essential component of the water repellent of the present invention.
Examples of the PFAG represented by (6) include those represented by the following (Formula 10). In the following (Formula 10), the n value is 1 ≦ n <23, preferably 1
-17.

[0057]

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The fluoroalkylalkoxysilane compounds represented by the above-mentioned general formulas (4) to (5), which are essential components of the water repellent of the present invention, are novel substances and can be produced using conventional CF ₃ (CF ₂ )
_{n - (CH 2) m -Si} (OR) 3 or _{C n F 2n + 1 -C x} H 2x -Si
Excellent stability and durability compared with perfluoroalkane compounds such as (R) _a (X) _3-a (see JP-A-9-169779) and imparting excellent water repellency to various substrate surfaces can do. For example, the fluoroalkylalkoxysilane compound, which is an essential component of the water repellent of the present invention, comprises only 1
The contact angle becomes 120 ° or more simply by treating the glass surface with a 2% alcohol solution (100 to 110 ° for the conventional product).
Degree), and excellent water repellency can be imparted.

The water repellent of the present invention is represented by the general formula (4)
It is used as a solution of (5) or a fluoroalkylalkoxysilane compound represented by the general formula (9). In the present invention, alcohols are preferred as the solvent, and in particular, contain 20% or more, preferably 50% or more of the same alcohol as the alcohol constituting aminoalkoxysilane, which is a starting material for producing these compounds. Are preferred. If the amount of alcohol is too small, the stability tends to be poor.

In the present invention, 2
When a mixture of two or more aminoalkoxysilanes is used, the same alcohol component as each alcohol constituting the alkoxy group of the aminoalkoxysilane is used in each case.
It is desirable to contain 0% or more. In the present invention, the solvent may be composed entirely of an alcohol, or may be composed using another desired solvent. In the present invention, it cannot be specified by the substances represented by the general formulas (4) to (5), but if it is within 50%, any other solvent may be used for application workability, drying property, etc. However, the mixing of water and the like should be within several percent.

When the water repellent of the present invention is used particularly for a windshield of an automobile or the like, a solvent which erodes rubbers, paints and the like is not suitable, and the solvent is preferably selected from alcohols.

In the water repellent of the present invention, when the essential components are those represented by the above general formulas (3) to (4), effective water repellency is 5% or less, usually 0.5 to 2%. Show. Further, in the water repellent of the present invention, the essential component is the general formula (5)
In the case of those represented by, because the perfluoroalkyl group is in the main chain, the general formula (4), the water-repellent performance tends to be lower than that of the side chain type represented by (9) However, it can be sufficiently used as a water repellent, or can be used as an auxiliary water repellent. That is,
The compound represented by the general formula (5) may be used in combination with an alkoxysilane perfluoroalkylalkoxysilane or a wax which is usually used as a water repellent.

[0063]

The present invention will be described below in more detail with reference to examples.

Reference Example 1 (Preparation Example of Water Repellent of the Present Invention) H ₂ N (CH ₂ ) ₃ Si (OEt) ₃ (3-aminopropyltriethoxysilane, TSL833, manufactured by Toshiba Silicone Co., Ltd.)
1) A solution of 6.63 g (30 mmol) in 50 g of ethyl alcohol (reagent, purity 99.5%) was placed in a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel. Charged and replaced with nitrogen. Then, while stirring with a magnetic stirrer, introducing nitrogen from the dropping funnel while introducing nitrogen, the perfluoro-1H,
15.18 g of 1H-nonanol glycidyl ether (manufactured by the applicant, purity: 99.9% PFAG-1C-8) (3.
0 mmol) was added dropwise at room temperature over 15 minutes, stirred for 2 hours, aged at 40 ° C. for 1 hour, and cooled to room temperature.

[0065]

Embedded image

The reaction product obtained by the above reaction was a colorless, transparent, low-viscosity liquid.

The reaction was carried out using the PFAG-1C-8 and TSL8.
In order to confirm that the reaction is a one-molecule reaction of
C (thin layer chromatography analysis) was carried out using the following two kinds of developing solutions. TLC plate: silica gel, Merck Kieselgel
60F254 Developing solution: (i). Confirmation of PFAG-1C-8 (petroleum benzene / ethyl acetate = 8/2) (ii). Confirmation of TSL8331 (petroleum benzene / ethyl acetate = 2/8) Any of the developing solutions described above In the PFAG-
1C-8, the spot of TSL8331 was not observed, and the absorption of 1593 cm ^-1 attributed to the NH ₂ group in TSL8331 disappeared from the FTIR of the product, indicating that the glycidyl group of PFAG-1C-8 was TSL833
It was confirmed that the reaction was an equimolar reaction in which one NH ₂ group reacted with one hydrogen atom.

1 to 3 show FTIR data of the reaction product and the starting material (raw material) of the above <Reference Example 1>. (1) FIG. 1 shows FTIR of the reaction product of the above <Reference Example 1>.
It shows the data. (2). FIG. 2 shows PFA which is a starting material of the above <Reference Example 1>.
8 shows FTIR data of G-1C-8. (3). FIG. 3 shows TSL which is the starting material of the above <Reference Example 1>.
9 shows FTIR data of 8331.

By the above reaction, the reaction solution is CF _3- (C
F ₂ ) ₇ —CH ₂ —O—CH ₂ —CH (OH) —CH ₂ —NH—
It was obtained as an ethanol solution containing 30% of (CH ₂ ) ₃ —Si (OEt) ₃ .

[0070] <Reference Example 2> using various PFAG in Reference Example 1 and the law (Preparation of water repellent of the present invention), C _n F _{2n + 1} is an essential component of the water repellent agent of the present invention - CH ₂ —O—CH ₂ —C
_{H (OH) -CH 2 -NH- (} CH 2) 3 -Si (OEt) 3 in ethanol was obtained. The concentration of the reaction solution as a reaction product was adjusted with ethyl alcohol. The results are shown in Table 1 below.

[0071]

[Table 1]

<Reference Example 3> (Preparation Example of Water-Repellent Agent of the Present Invention)_TwoN (CH_Two)_TwoN
H (CH_Two)_ThreeSi (OMe) _Three, {N- (2aminoethyl)-
3-aminopropyltrimethoxysilane, Toshiba Silicon
TSL-8340 @ 6.66g (30mmo
l) and ethyl alcohol into ethyl alcohol / methyl
Alcohol (reagent, purity 99.8%) = 1/1
The same method was used except that 50 g was used. No reaction products
It was a colorless, low-viscosity solution. About the reaction product
PFAG-1C-8 and T by TLC in the same manner as in Example 1.
The disappearance of the SL-834 spot was confirmed, and the
Also TSL-8340 NH_Two1599cm belonging to the group^-1
Of the PFAG-1C-8
And a single molecule reaction of TSL-8340 was confirmed.

The reaction solution obtained by the above reaction is CF _3- (CF
_{2) 7 -CH 2 -O-CH} 2 -CH (OH) -NH- (CH 2) 2
-NH- (CH _{2) 3} was obtained as a 30% solution of -Si (OMe) _3.

A compound similar to the above reaction product (the one having an n value of 8) (other n values) was prepared. The results are shown in Table 2 below. In Table 2, the symbol “B-8C1” is the one with the above-mentioned n value = 8.

[0075]

[Table 2]

Reference Example 4 (Preparation Example of Water Repellent of the Present Invention) In Reference Example 1, PFAG-1C-8 was replaced with the following (Chemical Formula 1)
Perfluoro 1,1,2,2 tetrahydrodecanol glycidiether shown in 2) (Purity 9
9.9%, 15.6 g (30 m) of PFAG-2C-8)
mol), and the same method was used.

[0077]

Embedded image

The reaction product is a colorless, transparent, low-viscosity solution.
In the reaction product that was found, PFAG-2C-
8 and TSL-8331 were not observed, and FT
1693cm by IR^-1Absorption had also disappeared. Reaction product
Is CF_Three(CH_Two)₇-CH_Two-CH_Two-O-CH_Two-CH
(OH) -CH _Two-NH- (CH_Two)_Three-Si (OEt)_Three30
% Ethanol solution.

A compound similar to the above-mentioned reaction product (the one having an n value of 8) (other n values) was also prepared. The results are shown in Table 3 below. In Table 3, the symbol “C-8”
“C2” is the above-mentioned n value = 8.

[0080]

[Table 3]

Example 1 A glass substrate was immersed and applied in a solution prepared by adjusting an ethyl alcohol solution containing 30% of “A8C1” of Reference Example 1 to 0.5 to 3% with ethyl alcohol, and then applied at room temperature for 1 to 2 minutes. After air-drying, the coated surface was wiped once or twice with a commercially available tissue paper, and the finger touch angle (Elmer contact angle measuring device, water droplet 4 μm) was measured. For comparison, a commercially available fluorine-based water repellent for automobiles (active ingredient 3%) (Comparative Example 1) and heptadecafluorodecyltrimethoxysilane [CF ₃ (CF ₂ ) ₇ CH ₂ CH]
₂ Si (OCH ₃ ) ₃ ] (TSL823 manufactured by Toshiba Silicone Co., Ltd.)
3) A 2% solution (Comparative Example 2), and the same procedure was performed for the case where 0.2% of the above TSL8331 was added to a 2% solution of TSL8333 (Comparative Example 3). The results are shown in Table 4 below.

[0082]

[Table 4]

As is evident from the above, the water repellent composition of the present invention shows a large contact angle at 0.5 to 3%, and is obtained by simply adding aminosilane to TSL8233, The contact angle was larger than that of the existing fluorine-based water repellent.

Examples 2 to 17 The various water repellent components prepared in Reference Examples 1 to 3 were adjusted to a concentration of 2% and applied to a glass substrate in the same manner as in Example 1 to compare the water repellency. did. The results are shown in Tables 5 and 6 below.
Shown in In addition, "fall inclination angle (degree)" in the table was measured using Kyowa Kagaku Co., Ltd. (AA type).

[0085]

[Table 5]

[0086]

[Table 6]

According to this example, when the perfluoroalkyl group becomes larger or smaller, the contact angle tends to be smaller, but this is within a range in which there is no problem in practical use. Note that a stable composition was obtained even when the ethyl alcohol in this example was changed to isopropyl alcohol,
Water repellency was not affected. Further, the water repellent of the present invention,
Even when the base was a PET film or the like, the same contact angle as glass was exhibited. In Comparative Examples 2 and 3, the reduction was 10% or more with respect to the PET film.

Example 18 A-8C1, B-8C1, obtained in Reference Examples 1, 3, and 4
Using C-8-C2, adjusted to 2% by the same method as in Example 1,
A sample was prepared by dip coating on a glass substrate. Then
These samples were compared for performance in a durability test. As comparative data, comparative samples 1 used in Example 1 were used.
3 was used.

The durability test was carried out by using the following cleaning liquid used for car washing and the like, according to the following procedure, with a contact angle and an inclination angle of 30 °.
The amount of water droplets starting to roll in ° (water droplet rolling property, unit μl) was compared before and after the treatment. The smaller the water droplet rolling property, the better. (i). Washing solution used (a) A stock solution of a car shampoo solution (manufactured by Wilson) was used (usually, the stock solution was diluted 60 times with water and used). (B) A stock solution of a window washer solution (manufactured by Wilson) was used (usually, the stock solution was used after diluting it five-fold with water). (ii). Endurance test procedure (1) Soak the stock solution of car shampoo solution in gauze
After rubbing 0 times, those washed with water and dried at room temperature were compared before and after the treatment. (2). After immersing in a stock solution of window washer solution for one week, washing with water and drying at room temperature were compared before and after the treatment.

The results of the durability test are shown in Table 7 below. Table 7
As shown in the above, the water repellent of the present invention exhibited excellent durability also in a car shampoo solution for washing a vehicle body and a window oil film washer solution for washing a windshield. Also,
The rolling properties of water droplets were good, and the property of falling naturally during running was recognized.

[0091]

[Table 7]

[0092]

According to the present invention, the following various advantages can be obtained. 1. The water repellent component comprising a perfluoro group-containing alkoxysilane compound having a novel structure of the present invention has an extremely simple production method and exhibits excellent water repellency. That is, the perfluoro group-containing epoxy compound (PFAG), which is a starting material, has a simple production method and can be obtained in high purity, so that the water repellent of the present invention is economical. 2. The water-repellent component comprising a perfluoro group-containing alkoxysilane compound having a novel structure according to the present invention has a low environmental load because an aliphatic alcohol-based compound is used as a solvent during synthesis from the production stage. 3. The water repellent of the present invention exhibits excellent water repellency to various substrates such as glass and PET. For this reason, it is useful, for example, as a water repellent for window glasses of automobiles.

[Brief description of the drawings]

FIG. 1 is an FTIR diagram of a reaction product of Reference Example 1.

FIG. 2 is an FTIR diagram of a starting material (monoepoxy compound) of the reaction of Reference Example 1.

FIG. 3 is an FTIR diagram of a starting material (aminoalkoxysilane compound) of the reaction of Reference Example 1.

Claims (8)

[Claims] 1. The fluoroalkoxysilane compound according to claim 1, wherein the N atom of the aminoalkoxysilane compound represented by the following general formula (1) has at least one monovalent bonding group represented by the following general formula (2). A water repellent containing an alkylalkoxysilane compound. <General formula (1)> HN (R ')-Y-Si (R) _a (X) _3-a ............ (1) (In the formula, R' is hydrogen or monovalent. R is a monovalent hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group or — (CH ₂ ) _y —NH—Y ′, Y ′ is a divalent hydrocarbon group,
y represents an integer of 1 to 4, and a represents an integer of 0 to 2. ) <Formula _{(2)> C n F 2n} + 1 -C x H 2x -O-CH 2 -CH (OH) -CH 2 - ............... (2) ( wherein, n 1 ≦ n <An integer of 23, and x represents an integer of 1 or 2.) 2. The two molecules of the aminoalkoxysilane compound represented by the following general formula (1) are bonded to a divalent bonding group represented by the following general formula (3) via respective N atoms. A water repellent comprising a fluoroalkylalkoxysilane compound, characterized by the following. <General formula (1)> HN (R ')-Y-Si (R) _a (X) _3-a ............ (1) (In the formula, R' is hydrogen or monovalent. R is a monovalent hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group or — (CH ₂ ) _y —NH—Y ′, Y ′ is a divalent hydrocarbon group,
y represents an integer of 1 to 4, and a represents an integer of 0 to 2. ) <Formula _{(3)> [-CH 2 -CH} (OH) -CH 2 -O-C n H 2n -C x F 2x -O-CH 2 -CH (O H) -CH 2 -] ...... (3) (In the formula, n is an integer of 1 ≦ n <23, and x is an integer of 1 or 2.) 3. A fluoroalkylalkoxysilane compound
The repellent material according to claim 1, wherein the product is represented by the following general formula (4).
Liquid medicine. <General formula (4)> C_nF_{2n + 1}-C_xH_2x-O-CH_Two-CH (OH) -CH_Two-N (R ')-Y-Si (R) _a (X)_3-a ………………………… (Four) 4. The water repellent according to claim 2, wherein the fluoroalkylalkoxysilane compound is represented by the following general formula (5). <Formula _{(5)> (X) 3} -a (R) a Si-Y-N (R ') - CH 2 -CH (OH) -CH 2 -O-C x H 2x - C n F 2n - C _x H _2x —O—CH ₂ —CH (OH) —CH ₂ —N (R ′) — Y—Si (R) _a (X) _3-a ………………… (5) 5. The water repellent according to the following general formula (4) and general formula (4)
Fluoroalkylalkoxysilane compound represented by (5)
Water repellent containing a substance. <General formula (4)> C_nF_{2n + 1}-C_xH_2x-O-CH_Two-CH (OH) -CH_Two-N (R ')-Y-Si (R) _a (X)_3-a …………………… (4) <General formula (5)> (X)_3-a(R)_aSi-YN (R ')-CH_Two-CH (OH) -CH_Two-OC_xH_2x− C_nF_2n-C_xH_2x-O-CH_Two-CH (OH) -CH_Two-N (R ')-Y-Si (R)_a(X)_3-a (5) (wherein R ′ is hydrogen or a monovalent hydrocarbon group, and R is a monovalent
Hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group
Or-(CH_Two)_y-NH-Y 'and Y' are divalent hydrocarbon groups,
n is an integer of 1 ≦ n <23; y is an integer of 1 to 4;
Indicates an integer of 2. ) 6. A fluoroalkyl represented by the general formula (4):
Alkoxysilane compound, in an alcohol solvent, the following
An aminoalkoxysilane represented by the general formula (1)
The fluoroalkyl group-containing compound represented by the general formula (6)
Prepared by reacting with a oxy compound.
The water repellent according to claim 3, which is: <General formula (1)> HN (R ')-Y-Si (R)_a(X)_3-a ... (1) (wherein, R 'is hydrogen or a monovalent hydrocarbon group, and R is a monovalent hydrocarbon group.)
Hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group
Or-(CH_Two)_y-NH-Y 'and Y' are divalent hydrocarbon groups,
y represents an integer of 1 to 4, and a represents an integer of 0 to 2. <General formula (6)>(Wherein, n is an integer of 1 ≦ n <23, x is an integer of 1 or 2
Is shown. <General formula (4)> C_nF_{2n + 1}-C_xH_2x-O-CH_Two-CH (OH) -CH_Two-N (R ')-Y-Si (R) _a (X)_3-a ………………………… (Four) 7. A fluoroalkylalkoxysilane compound represented by the general formula (5) is obtained by mixing an aminoalkoxysilane represented by the following general formula (1) and an aminoalkoxysilane represented by the following general formula (7) in an alcohol solvent. The water repellent according to claim 4, which is prepared by reacting a fluoroalkyl group-containing diepoxy compound. <General formula (1)> HN (R ')-Y-Si (R) _a (X) _3-a ............ (1) (In the formula, R' is hydrogen or monovalent. R is a monovalent hydrocarbon group, X is an alkoxy group, Y is a divalent hydrocarbon group or — (CH ₂ ) _y —NH—Y ′, Y ′ is a divalent hydrocarbon group,
y represents an integer of 1 to 4, and a represents an integer of 0 to 2. <General formula (7)> (In the formula, n represents an integer of 1 ≦ n <23, and x represents an integer of 1 or 2.) <General formula (5)> (X) _3-a (R) _a Si-YN (R ′) _{) -CH 2 -CH (OH) -CH} 2 -O-C x H 2x - C n F 2n -C x H 2x -O-CH 2 -CH (OH) -CH 2 -N (R ') - Y −Si (R) _a (X) _3-a ………………………… (5) 8. The water repellent according to claim 6, wherein the alcohol component of the alcohol solvent is the same as that forming the alkoxy group of the aminoalkoxysilane compound represented by the general formula (1).